Kesterite-type Cu2ZnSnS4 was synthesized from the corresponding binary sulfides by a mechanochemical route in a planetary ball mill. The reaction progress during this milling step was followed within a time range of 10-180 min by powder X-ray diffraction. In addition, the crystallization of the milled material was studied in situ by high-temperature X-ray diffraction methods in the temperature range of 300500 degrees C. Significant disorder (cation distribution) was observed at 500 degrees C, strongly decreasing during cooling down to ambient temperature with a rate of 60K/h. (C) 2016 Elsevier Ltd. All rights reserved.